Method of treating an oil or gas well with biodegradable low toxicity fluid system

ABSTRACT

A method of treating a well consists of introducing into the wellbore a biodegradable fluid system containing a fatty acid ester, such as methyl soyate. The fluid system may further contain a lactic acid ester, such as ethyl lactate, and/or a nonionic surfactant. The fluid system may be used in displacement, well remediation and stimulation as well as additional, alternative applications such as the cleaning of surface and/or downhole equipment.

SPECIFICATION

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 10/985,458, filed on Nov. 10, 2004 now U.S. Pat.No. 7,231,976.

FIELD OF THE INVENTION

The invention relates to a process of treating an oil or gas well havinga wellbore with a biodegradable fluid system containing a fatty acidester. The biodegradable fluid system may be in the form of amicroemulsion.

BACKGROUND OF THE INVENTION

Stimulation refers to the treatment of geological formations to improvethe recovery of hydrocarbons. Common stimulation techniques include wellfracturing and acidizing operations.

Fracturing of the formation is accomplished by pumping fluids into theborehole of an oil or gas well under high pressure to create fracturesin the rock formation surrounding the wellbore. The fractures radiateoutwardly from the wellbore, typically from a few to hundreds of meters,and extend the surface area from which oil or gas drains into the well.

Typically, the fracturing fluid is a crosslinked polymer that has beengelled to increase its viscosity. Crosslinked gels are able to withstandthe high temperature conditions commonly found in deeper oil and gaswells with little reduction in viscosity. After the fracturing fluid isinjected into the formation to produce the fracture, the viscosity ofthe fluid is reduced by gel breakers. Such components break down thegelled fluid so that it can be easily pumped and removed from the well.Often, breaker catalysts are used to activate the gel breaker.

In certain formations, aqueous acid solutions can be used to improve thepermeability of the formation, thereby increasing production. Theseacids are often combined with the polymer gels used in fracturing toprovide an acid fracturing fluid. One of the benefits of combining theaqueous acid solutions with gelled fracturing fluids is that the gelledfluid inhibits or retards the reaction of the acid with the formation.This is beneficial in that the acid would otherwise react too quickly,depleting the acid with very little penetration of the formation. Oncein place, the viscosity of the fluid is reduced so that the acid isreleased to react with formation damage or other skin present at theface of the newly formed fractures and improving the permeability of theproducing strata.

In addition to fracturing and acidizing operations, stimulation furtherencompasses techniques for enhancing oil recovery as well as watercontrol treatments. In the latter, the flow of excess water is preventedwhile the flow of produced hydrocarbons from the well is enhanced. Forinstance, U.S. Pat. No. 5,228,812 and U.S. Patent Application No.US2004/0177957A1 discloses a chemical treatment that selectively reduceswater production by the use of relative permeability modifiers (RPMs).RPMs are generally water soluble polymers having a charged end whichassists in binding of the RPM to the geological rock formation.

Stimulation methods often include the use of spearhead fluids that aretypically composed of an aqueous base fluid and chemical additives.Spearhead fluids precede the introduction of stimulation fluids.Spearhead fluids, for instance, may precede the introduction of RPMs.The spearhead fluid thereby removes heavy oil deposits in the nearwellbore and oil films in the pore spaces of the rock. The RPM is thenintroduced and is capable of more strongly adhering to the rock.

In contrast to stimulation, remediation refers to the removal ofunwanted deposits from the wellbore and production equipment.Remediation includes hydrogen sulfide mitigation. Such unwanted depositsform and/or accumulate in the wellbore, production and recoveryequipment and well casing. For example, highly toxic hydrogen sulfide isproduced during the decomposition of organic matter. In addition tohydrogen sulfide, other undesirable downhole products form such asscale, paraffins, fines, pipe dope, sulfur, heavy oil tar by-productsand water blocks. Such accumulated deposits affect productivity and aretypically removed prior to cementing or the introduction of completionfluids into the wellbore. Remediation treatment fluids are furthertypically used to remove such undesired deposits prior to theintroduction of stimulation fluids.

Upon the completion of drilling and cementing operations, it is oftendesired to displace the drilling fluid system with a completion fluidsystem. Completion often requires the use of a packer fluid in theannulus between the casing and the production tubing. Well completiondesigns and reservoir conditions govern acceptable levels of particlecontent in packer fluids. The required cleanliness of this fluid canvary from several hundred Nephelometric Turbidity Units (NTU) down to10-20 NTU.

Displacement of a drilling fluid with a completion fluid may beperformed in several steps. Typically, the drilling fluid is firstdisplaced by a casing cleaning fluid. Treatment with seawater normallyfollows. The seawater may then be displaced by a packer fluid. Completedisplacement of a fluid by another fluid by use of hydraulic force isdifficult to achieve in the annulus. In order to more efficientlydisplace the drilling fluid with a packer fluid, cleaning fluids with avariety of chemical additives are pumped between the drilling fluid andthe packer fluid. The chemical additives serve to disperse and break-upsolid components within the drilling fluid. In addition, they serve todecrease surface activity between the two fluids.

Well treatment fluids presently used for stimulation and remediation aswell as fluids for removing drilling muds from the wellbore, prior tocementing or introduction of a completion brine, are either notbiodegradable or are less efficacious than desired. There is a continuedneed for more effective methods and systems for drilling fluiddisplacement, enhancement of oil recovery, wellbore remediation andformation stimulation. In particular, there is a need for new systemsthat are biodegradable.

SUMMARY OF THE INVENTION

Improved efficiency in well remediation and stimulation is evidenced bythe introduction of a biodegradable fluid system into the wellbore. Thefluid system has applicability in the removal of pipe dope andhydrocarbons, oil based, and synthetic oil based drilling muds and thedispersement of paraffins and asphaltenes. It may further be used as adisplacement spacer system, either as a single spacer or as a multiplespacer in conjunction with a second fluid, for the removal ofoil/synthetic oil based mud cake and hydrocarbons prior to cementing orprior to introduction of a completion brine.

In addition, the fluid system of the invention is useful as a spearheadfluid for the removal of unwanted deposits or hydrocarbons prior to theintroduction of a stimulation (or other well treatment) fluid.

Further, the fluid system for use in the invention is of assistance inwater control and as a breaker catalyst to decrease the viscosity offracturing fluids and other gelled well treatment fluids upon loweringof the pH. Alternatively, the fluid system may function with enzymebreakers. As the pH of the fluid system is decreased, the enzymes areactivated which causes a decrease in viscosity of the fracturing fluidsor other gelled well treatment fluids.

The biodegradable fluid system is further useful in the displacement ofsynthetic and oil based drilling mud systems from the annulus andcasing.

The fluid system contains a fatty acid ester. The preferred fatty acidester is a C₁-C₄ alkyl ester of a C₁₆-C₂₀ fatty acid such as an ester ofoleic or linoleic acids. In a preferred embodiment, the fatty acid esteris methyl soyate.

The fluid system may further contain a lactate ester and/or asurfactant. The lactic acid ester is preferably a C₁-C₄ ester of lacticacid, such as ethyl lactate. The surfactant is preferably a nonionicsurfactant.

The fluid system may contain an emulsifying agent. The emulsifying agentis typically anionic, non-ionic, or amphoteric.

The fluid system may further consist of an oil-in-water microemulsionwhich may, optionally, contain an alcohol.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The fluid system used in the invention displaces synthetic and oil baseddrilling mud systems from the annulus and casing as well as increasesthe production of hydrocarbons from oil and gas wells by managingundesirable downhole products encountered during the production ofhydrocarbons from such reservoirs. The fluid systems of the inventionexhibit high flash points, generally in excess of 145° C. In addition,the fluid systems of the invention have low volatile organic compounds(VOCs) and exhibit very low aquatic toxicity. Thus, the fluid systems ofthe invention are especially useful in environmentally sensitive areasas well as in areas where a high flash point is necessary.

The system contains a fatty acid ester. It may further be combined withone or more emulsifiers and water to form a stabilized oil-in-watermicroemulsion. The microemulsion exhibits stability at hightemperatures. For instance, a clear stable microemulsion with a 30volume percent loading of the fluid system has been demonstrated to bestable at 82° C. and to 4° C. for a period of four hours.

Suitable fatty acid esters are those C₁-C₄ esters of C₁₆-C₂₀ fatty acidsincluding edible vegetable oils. Such oils may have a melting point of−10° C. or less. Preferred edible vegetable oils are selected from thegroup consisting of corn, coconut, mustard, palm kernel oil, neem, nigerseed, olive, peanut, poppy seed, safflower, rapeseed, sesame, soybean,sunflower seed, wheat germ oil and other polyunsaturated containing oils(such as oleic acid, linoleic acid, erucic acid and linolenic acid).

The C₁₆-C₂₀ fatty acid ester may further be a mixture of oils. Ediblevegetable oils containing a mixture of about 70 to about 90 weightpercent oleic and linoleic acids are often preferred. Soybean oil, whichis comprised principally of oleic and linoleic acids, is a preferredC₁₆-C₂₀ fatty acid. A methyl ester is the preferred C₁-C₄ group. Aparticularly fatty acid ester is soybean methyl ester or soy methylester. Soy methyl ester is obtained from the esterification of soybeanoil. Such fatty acid esters are non-toxic and biodegradable.

The fatty acid ester may further be combined with a lactate ester. Theresulting blend may be used in conjunction with a co-solvent blend. Thelactic acid ester is preferably a C₁-C₄ ester of lactic acid. ExemplaryC₁-C₄ alcohols for producing the lactic acid ester include methanol,ethanol, propanol, isopropanol, allyl alcohol, butanol, 3-buten-1-ol,t-butanol and sec-butanol. (Such alcohols are further the preferredalcohols for producing the fatty acid esters.) In a particularlypreferred embodiment, the lactic acid ester is ethyl lactate. Ethyllactate is the ester of natural lactic acid produced by fermentation ofcorn-derived feedstock. Like the fatty acid esters, lactic acid estersare 100% biodegradable, breaking down into carbon dioxide and water,non-toxic, and renewable.

When present, the lactic acid ester is present at about 20 to about 75weight percent and the fatty acid ester at about 10 to about 80 weightpercent of the blend. In still other embodiments, the two co-solventsare each present at about 40 to about 60 weight percent of thecomposition. In a preferred embodiment, the weight ratio of lactic acidester:fatty acid ester is between from about 35:65 to 65:35, preferably50:50.

The fatty acid ester may further be combined with a surfactant. Theresulting fluid may further contain the lactic acid ester set forthabove. In a preferred embodiment, the surfactant is nonionic. Nonionicsurfactants with HLB between from 1 to about 30 are preferred, mostpreferably those having a HLB between from about 10 to about 20.Preferred nonionic surfactants include oxyalkylated alkyl phenols suchas octylphenol polyethylene oxide ethers and nonylphenol polyethyleneoxide ethers as well as linear alcohol polyethylene oxide ethers andsorbitan monooleate polyethylene oxide ethers. Such nonionic surfactantsinclude those sold under the commercial name of TERGITOL, TRITON, BRIJand MAKON. When present, the weight percent of the nonionic surfactantbased on the total weight of C₁-C₄ ester of a C₁₆-C₂₀ fatty acid andsurfactant is between from about 1 to about 8 percent.

The fluid system may further contain thixotropic agents and pHadjusters, when needed. For instance, the fluid systems may containbetween 0 to about 10 weight percent of thickener. Preferred thixotropicagents are polysaccharide derivatives having nonionic functionalitiessuch as alkyl alcohol or ether groups. Exemplary thickeners includemethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,hydroxypropyl methylcellulose, cornstarch, hydroxyethyl cornstarch, andhydroxypropyl cornstarch.

The fluid system may be a homogeneous liquid or gel at 0° C. It mayfurther have a flash point in excess of 60° C., preferably in excess of66° C.

The fluid system can also be used as a concentrate, and as such, it canbe admixed with up to about 30 weight percent water prior to use. Thefluid system may further be emulsified prior to use.

In particular, the fluid system used in the invention may be in the formof a microemulsion, defined as a multiphase system consisting of water,co-solvent blend, emulsifier(s), and alcohol, and is a transparent andthermodynamically stable liquid solution. Microemulsions can beconsidered as small-scale versions of emulsions, i.e., droplet typedispersions either of oil-in-water with an average particulate sizeranges in the order of about 5 to about 50 nm in drop radius. Inemulsions, the average drop size grows continuously with time so thatphase separation ultimately occurs. The drops of the emulsion aregenerally large (>0.1 microns) and often exhibit a milky or cloudy,rather than a translucent, appearance as seen in microemulsions.

The emulsifying agent lowers the interfacial tension between oil andwater to produce a sufficiently small droplet size, from about 3 micronsto about 20 microns, preferably about 10 microns or less in diameter.The emulsifier should be capable of creating an oil-in-watermicroemulsion upon combination with an appropriate quantity of water.Preferred emulsifiers are biodegradable and have an HLB(hydrophile-lipophile balance) value between from about 8 to about 18.

When employed, such emulsifiers may be present in the produced emulsionat a concentration in the range of about 200 ppm to about 10,000 ppm.

The emulsifiers can be anionic, nonionic, amphoteric, as well asmixtures thereof. Blends of both non-ionic and anionic emulsifiers havebeen found to decrease droplet size in most instances. Where such ablend is used, a preferred ratio of non-ionic to anionic emulsifier isabout 5/95 to about 95/5, preferably about 50/50 to about 85/15.

Any suitable, non-toxic anionic emulsifier may be used in such blends.Preferred anionic emulsifiers include, but are not necessarily limitedto those selected from the group consisting of alkyl sulfates, alkanesulfonates, alkyl aryl sulfonates and phosphate esters comprising about8 to about 18 carbon atoms, preferably about 8 to about 12 carbon atoms.

Suitable anionic emulsifiers include the sodium alkyl benzene sulfonatessulfosuccinic acid esters such as sodium dioctyl sulfosuccinate, and thelike. Preferred is dioctyl sulfosuccinate having an HLB value greaterthan about 13.

Suitable non-ionic emulsifiers are those based on fatty alcohols. Forinstance, a preferred non-ionic emulsifier is of the fatty alcoholethoxylate type such as one having 6-mole ethoxylation on a 12-carbonalcohol. An example of a particularly suitable fatty alcohol ethoxylateis tallow alcohol ethoxylate containing 2 or 3 moles of ethylene oxide.

Further suitable as the nonionic emulsifiers are alkyl and alkylarylpolyether alcohols such as linear or branched polyoxyethylene alcohols,more preferably linear polyoxyethylene alcohols, comprising (a) fromabout 8 to about 30, preferably about 8 to about 20, carbon atoms, and(b) comprising about 3 to about 50 moles, most preferably about 3 toabout 20 moles, ethylene oxide. Most preferred non-ionic emulsifiers arelinear polyoxyethylene alcohols having from about 13 to about 15 carbonatoms and comprising about 10 moles ethylene oxide. Further, preferredemulsifiers include nonylphenol ethoxylate having a HLB value of about16 and comprising 20 ethylene oxide units per molecule, octylphenolethoxylate having an HLB value greater than 13.5, and nonylphenolethoxylate having a HLB value greater than 13.

In another preferred embodiment, the non-ionic emulsifiers are acombination of alkylaryl ethoxylate and a polyethylene glycol (PEG)ester of fatty acids. Preferably, the alkylaryl ethoxylate is octyl,nonyl or dodecylphenol with 3 to 13 moles of ethylene oxide, while thePEG ester is of molecular weight range 200-600 with either one or twomoles of unsaturated fatty acids.

Further preferred as oil-in-water emulsifiers are polyoxyethylenesorbitan monopalmitate, polyoxyethylene sorbitan monostearate,polyoxyethylene sorbitan monooleate, linear alcohol alkoxylates, alkylether sulfates, linear nonyl-phenols, dioxane, ethylene glycol andethoxylated castor oils such as polyethylene glycol castor oil,dipalmitoylphosphatidylcholine (DPPC), polyoxyethylene (8.6) nonylphenyl ether, ethylene oxide sulfonates (i.e., alkylpropoxy-ethoxysulfonate), alkyl propoxy-ethoxysulfate,alkylarylpropoxy-ethoxysulfonate and highly substituted benzenesulfonates.

Illustrative amphoteric emulsifiers suitable for present purposes arepolyethoxyline amine and oxyethylated sodium salts.

While it is acknowledged that the emulsifiers outlined above cover awide range of physical properties and provide wide rangingemulsification abilities, a balance between two quite differentemulsifiers can produce a far greater effect than an intermediateemulsifier. For instance, especially desired results are obtained by useof a fatty alcohol and dioctyl sodium sulfosuccinate.

The microemulsions may further contain a sufficient amount of arelatively strong acid to lower the pH of the fluid system to about 4 orless, preferably to about 2 or less to about 3 or less, and mostpreferably to about 1 or less. Relatively strong acids include, but arenot necessarily limited to, phosphoric acid, hydrochloric acid, sulfuricacid, nitric acid, and the like. A preferred acid is phosphoric acid.

The alcohol component of the microemulsion serves as a coupling agentbetween the co-solvent blend and the emulsifier, thereby stabilizing themicroemulsion. The alcohol also lowers the freezing point of the welltreatment microemulsion. Although isopropanol is presently preferred,alternative suitable alcohols include mid-range primary, secondary andtertiary alcohols with between 1 and 20 carbon atoms, such as t-butanol,n-butanol, n-pentanol, n-hexanol and 2-ethyl-hexanol. Other freezeprevention additives can additionally or alternatively be added, such asdetergent range alcohols ethoxylate, ethylene glycols (EG), polyethyleneglycols (PEG), propylene glycols (PG) and triethylene glycols (TEG),with triethylene glycol being presently preferred.

The microemulsion preferably comprises from 0 wt % to about 15 wt %strong acid; about 10 wt % to about 70 wt %, preferably about 65 wt %emulsifier(s); from about 10 to about 50 wt % of lactate ester/fattyacid ester blend; from about 25 to about 45 wt. % alcohol and, theremainder, water. The microemulsion may further optionally include asalt.

The addition of a salt to the fluid system reduces the amount of waterneeded and also lowers the freezing point of the well treatmentmicroemulsion. Among the salts that may be added are NaCl, KCl, CaCl₂,and MgCl. Others suitable salts can be formed from K, Na, Br, Cr, Cs andBi metals.

The microemulsions may be prepared by subjecting the emulsifier(s),alcohol and optional components to high intensity shear at roomtemperature, typically for about 5 to 10 minutes. The blend of lacticacid ester and fatty acid ester is then added and shearing is continued.Water is then added, typically after about 5 to 10 minutes. Theresulting microemulsion is typically colorless.

Furthermore, it will be understood that in some applications, it may bedesirable to introduce the blend of lactic acid ester and fatty acidester blend downhole where it will be combined with separately injectedwater and water-based materials, such as emulsifier(s) and alcohol, toform the microemulsion in situ.

In well remediation applications, the fluid system is preferablyinjected directly into the wellbore through the production tubing orthrough the use of coiled tubing or similar delivery mechanisms. Oncedownhole, the well treatment fluid system remedies damage caused duringwell treating such as, for instance, by stimulation fluids and drillingfluid muds, by dispersing and removing fines, paraffin and/or asphaltenedeposits, sulfur, pipe dope and unwanted hydrocarbons, such as heavy oiltar by-products and water blocks, from the formation and wellbore.

The fluid system can further be used for hydrogen sulfide mitigation. Ina preferred embodiment, the fluid system is injected into the wellboreso that escaping hydrogen sulfide gas is “stripped” through the system.Preferably, the fluid system is periodically injected into problem wellsto mitigate hydrogen sulfide production. Alternatively, the fluid systemmay be injected downhole via capillary tubing on a continuous basis. Inyet another alternate embodiment, the fluid system may be placed in acontainer that is placed in fluid communication with the hydrogensulfide. The interaction between the fluid system and the hydrogensulfide neutralizes the enhancement of oil recovery and is useful inhydrogen sulfide, leaving an inert sulfur compound as a product of thereaction. Some or all of the water in the fluid system may further bereplaced with a known hydrogen sulfide scavenger. For example, manycyclic amines, such as triazines and hexamines, can be used incombination with water to further improve hydrogen sulfide mitigation.

The well treatment fluid system can also be used in stimulationoperations. In fracturing operations, for example, proppant material canbe added to the system before injection downhole. The well treatmentfluid system can also be used to deliver acids during acidizingoperations. Acids commonly used include hydrochloric, acetic, formic,and hydrochloric-hydrofluoric acids.

When a microemulsion is desired, the co-solvent blend and emulsifyingagent and alcohol may be combined with an acidified carrier fluid toprepare a microemulsion suitable for acidizing operations. Suchmicroemulsions include about 0.2%-15% by volume of the blend and about3%-28% by volume of acid. In a particularly preferred embodiment, themicroemulsion includes about 0.2%-15% of the blend and about 15% byvolume of hydrochloric acid. The concentration of the well treatmentmicroemulsion in gelled fluids lowers the friction created by contactwith conduits, thereby facilitating the injection and withdrawal of thewell treatment microemulsion.

The fluid system of the invention is useful in the enhancement of oilrecovery and has applicability as a spearhead fluid and thus may beintroduced prior to the introduction of a well treatment fluid. Forinstance, the fluid system is useful as a spearhead fluid to removeproduced hydrocarbons prior to a water control treatment. This treatmentfurther serves to prevent breakage or emulsification of the subsequentlyinjected water control fluid due to mixing with the produced oil.

The system is further efficacious in the alleviation of water blocks,the removal of excess water and the lowering of pore pressure in theformation.

The fluid system used in the invention is suitable for the reduction ofthe viscosity of any well treating gelled fluid. For instance, the welltreatment fluid system is useful as a breaker catalyst for highlyviscous crosslinked gels to lower viscosity fluids by lowering the pH ofthe system. This occurs by the conversion of the lactic acid ester tolactic acid that, in turn, lowers the pH. The lowering of the pH servesto reduce the viscosity of the gelled fluid by reversing thecrosslinking of the fracturing fluids. Desired materials, such as oiland gas, thereafter more easily flow into the wellbore.

In addition, where an enzyme breaker is used, the use of the fluidsystem of the invention causes a decrease in pH over time. As the pH isdecreased, the enzymes are activated. Upon activation, the enzymesfunction to break the gel. Thus, the solvent system may be utilized toactivate gel breakers, such as enzymes, to reduce the viscosity of afracturing fluid or gelled fluid system.

In a preferred mode, the fluid system is used to displace the drillingfluid with the completion fluid by being pumped into the well prior tointroduction of packer fluid, when used. The fluid system has particularapplicability in the removal of synthetic based oil muds (SOBM) and oilbased drilling muds (OBM) from the wellbore casing, tubing and downholeliners in light of its ability to more readily break down emulsifiersand other additives present in the mud. In a particularly preferredembodiment of the invention, the fluid system is a microemulsion used toremove OBM/SOBM drilling mud fluids. When used as a microemulsion, theemulsifier should be selected according to whether oil or water baseddrilling fluids is used.

The system is further effective at decreasing the density of filtercakes during high pressure injection of gelled fluids into the wellbore.

The fluid system may also be used for other applications such as toclean surface and downhole equipment.

The following examples will illustrate the practice of the presentinvention in its preferred embodiments. Other embodiments within thescope of the claims herein will be apparent to one skilled in the artfrom consideration of the specification and practice of the invention asdisclosed herein. It is intended that the specification, together withthe example, be considered exemplary only, with the scope and spirit ofthe invention being indicated by the claims that follow.

EXAMPLES

In the Examples, the following components were used:

SoyGold 1000, a product of AG Environmental, containing soybean methylester and having a flash point in excess of 150° C., a VOC of 7.29% (64g/l), and a boiling point of 333° C.;

SoyGold 2000, a product of AG Environmental, containing soybean methylester and 3 weight percent surfactant and having a flash point in excessof 150° C., VOC of 4.3 g/1; and a boiling point of 334° C.;

VertecBio Gold #1, product of Vertec Gold, containing 50 volume percentethyl lactate and 50 volume percent soybean methyl ester and having aflash point of 65.6° C., a VOC of 604 g/l and a boiling point of 144.4°C.;

Paravan 25, a terpene-based solvent, commercially available from BJServices Company;

Synperonic 91/6 is a fatty alcohol ethoxylate, commercially availablefrom Uniqema;

Monawet MO-70R is composed of dioctyl sodium sulfosuccinate andpropylene glycol, commercially available from Uniqema;

Monawet MM-80 is composed of a sulphosuccinate, commercially availablefrom Uniqema;

Nova Plus is a drilling fluid mud of M-I Swaco;

EOG is drilling fluid mud of Enron Oil & Gas; and

Synteq is a drilling fluid mud of Baker Hughes Inteq.

All percentages are weight percent unless otherwise noted.

Examples 1-4

Pipe dope removal efficiency studies were conducted with four differentpipe dope materials. A Chan 35 viscometer rotor sleeve and ring wereweighed clean, W1. Each of the test pipe dope materials were coated ontothe pre-weighed Chan 35 viscometer sleeve and the weight of the sleeveand pipe dope were recorded, W2. The sleeve was placed back onto theviscometer without the interior bob. The test fluid system (SoyGold 2000and VertecBio Gold #1) were heated to 140° F. The heater cup was thenplaced separately around the Chan 35 pipe dope coated sleeve until thefluid reached the marked fluid line.

After the fluid level was reached, the Chan 35 was turned on for 20minutes at the 200 rpm setting. After the twenty minute reaction period,the Chan 35 was turned off, the heater cup lowered and the Chan 35sleeve was allowed to drain for two minutes. After the two-minute drainperiod, the sleeve was removed from the viscometer and weighed, W3. Thepercent pipe dope removal efficiency was calculated by the followingformula:(W2−W3)/(W2−W1)×100.Results of the pipe dope removal tests are summarized in Table 1 below.

TABLE I Pipe Dope Removal Efficiency Studies at 140° F. for 20 MinutesExample SoyGold VertecBio No. Pipe Dope 2000 Gold #1 Paravan 25 1 APIModified High 72.1%   90% 92% Pressure High Temperature Thread 2 326 OCRModified 68% 91% 84% 3 Eco Lubeseal Thread 97% 96% 95% Compound 4Bestolife 2000 89% 97% 95%

VertecBio Gold #1 and SoyGold 2000 were as efficient as Paravan 25 inthe removal of pipe dope from the Chan 35 sleeve. VertecBio Gold #1 wasshown to be more efficient than the Paravan 25 solvent and the SoyGold2000 system in removing the four test pipe dope materials.

Examples 5-12

Chan 35 tests were conducted to determine mud removal efficiency from ametal surface and the cleaning efficiencies of two bio-based fluidsystems in comparison to Paravan 25 solvent system. The studies wereconducted with seven oil based and synthetic oil based drilling muds andone thick produced oil sample at temperatures of 70° F. and 150° F.

The Chan 35 tests procedure involved: (1) weighing the Chan 35 rotorwithout the “bob” to determine the initial weight of the clean rotor,W1; (2) mixing each of the mud systems for 30 minutes and transferring auniform sample to a Fann cup; and, if required, (3) heating both thetest mud/hydrocarbon and the test solvent to 180° F. for a period of 20minutes; (4) raising the Fann cup with the well mixed mud/hydrocarbonsample to the scribed line on the rotor and allowing the samples tostand under static conditions for 10 minutes; (5) lowering the mud fromthe rotor and allowing it to drip for two minutes; (6) wiping the bottomsurface of the rotor clean and weighing the ring and rotor with auniform mud coating upside down on a balance and then recording theweight, W2; (7) replacing the rotor on the Chan 35 and placing the rotorcovered with a uniform layer of mud/oil sample in a test cup containingthe test solvent at the desired test temperature; (8) rotating the rotorat 200 rpm for 10 minutes and then removing it from the test solution;(9) allowing the rotor to drip for two minutes and wiping the bottom toremove any drops without removing the test mud or remaining hydrocarbon;(10) removing the rotor from the Chan 35 and weighing it upside down,W3; (11) repeating the process until W3 values at 20 and 30 minutes havebeen obtained; (12) calculating the % mud removal using the W1, W2, andW3 values.

The % removal efficiencies (RE %) of the test solvents at 70° F. and150° F. were calculated by the following formula:RE%=(W2−W3)/(W2−W1)×100

The initial rheologies of the test muds samples and producedhydrocarbons utilized in the displacement spacer study were measured atroom temperature as a key indicator to mud properties and overallcondition for displacement. The rheology data of the mud samples, asrecorded from the Chan 35 rheometer at 70° F., are set forth in Table IIbelow.

TABLE II Chan 35 Rheology Data On The Test Muds/Hydrocarbon Systems At70° F. Example No. 600/300 200/100 60/30 6/3 Gel/10 min Gel 5 12.5 ppgNova Plus SOBM 64/34 24/12 12/7  2/1 1/1 6 14.0 ppg Nova Plus SOBM 48/2819/12 8/7 3/2 3/5 7 14.0 ppg Synteq OBM 67/36 24/14 9/6 4/3 3/6 8 17.0ppg Synteq OBM >320/217   152/79  50/27 8/5  8/17 9 15.3 ppg EOG OBM217/123 62/33 27/20 8/5 6/8 10 15.0 ppg Exxon Mobil OBM 115/66  47/2517/10 4/3  5/12 11 15.3 ppg US Encorp 178/95  66/37 25/15 7/5  9/13 12Exxon Mobil East Breaks Produced Oil 122/63  43/22 12/7  2/1 1/1

Table III and Table IV detail the results of the displacement studiesconducted with the three displacement solvent systems at 70° F. and 150°F.

TABLE III Oil Based and Synthetic Oil Based Drilling Mud RemovalEfficiencies (% MRE) At Room Temperature Ex. Drilling Mud SoyGoldSoyGold VertecBio No. System 1000 2000 Gold #1 Paravan 25 5 12.5 ppgNova Plus — 10 min - 85% 10 min - 89% 10 min - 90% 6 14.0 ppg Nova Plus10 min - 65% 10 min - 95% 10 min - 96% 10 min - 95% 7 14.0 ppg Synteq 10min - 75% 10 min - 90% 10 min - 97% 10 min - 90% 8 17.0 ppg Synteq — 10min - 1.18% 10 min - 81% 10 min - 82% 20 min - 3.1% 20 min - 93% 20min - 88% 30 min - 7.1% 9 15.3 ppg EOG — 10 min - 86% 10 min - 25% 10min - 91% 20 min - 93% 20 min - 34% 30 min - 38% 40 min - 40% 10 15.0ppg — 10 min - 20% 10 min - 96% 10 min - 90% ExxonMobil 20 min - 32% 30min - 46% 40 min - 50% 11 15.3 ppg US Encorp — 10 min - 16% 10 min - 81%10 min - 91% 20 min - 21% 20 min - 83% 25 min - 98% 12 Exxon Mobil East— 10 min - 90% 10 min - 90% 10 min - 90% Break Produced Oil

TABLE IV Oil Based and Synthetic Oil Based Drilling Mud RemovalEfficiencies (% MRE) at 150° F. Ex- ample SoyGold VertecBio No. 2000Gold #1 Paravan 25 Drilling Mud System 5 12.5 ppg 10 min - 91% 10 min -91% 10 min - 82% Nova Plus SOBM 6 14.0 ppg 10 min - 71 10 min - 93% 10min - 93% Nova 20 min - 79% Plus SOBM 7 14.0 ppg 10 min - 87% 10 min -10 min - 74% Synteq 100% 8 17.0 ppg 10 min - 10 min - 90% 10 min - 91%Synteq 10.8% 20 min - 17.6% 30 min - 23.4% 9 15.3 ppg 10 min - 86% 10min - 85% 10 min - 88% EOG 20 min - 94% 10 15.0 ppg 10 min - 18% 10min - 91% 10 min - 88% ExxonMobil 20 min - 43% 20 min - 90% 11 15.3 ppgUS 10 min - 50% 10 min - 88% 10 min - 91% Encorp 20 min - 84% 20 min -93% Produced Oil 12 Exxon Mobil 10 min - 90% 10 min - 90% 10 min - 90%East Break Produced Oil

VertecBio Gold #1 was as efficient in mud removal at room temperatureand 150° F. as the Paravan 25 solvent. The % MRE data shows theVerterBio Gold #1 was much more efficient in mud removal at roomtemperature and 150° F. than the SoyGold 2000 system. The removalefficiency from the Chan 35 rotor sleeve at 70° F. was from 85% to 95%.The removal efficiency at 180° F. was from 88% to 97%. The fluid systemcan be used as a displacement spacer system, either as a single spaceror as a multiple spacer in connection with a second fluid, toeffectively remove oil/synthetic oil based mud cake and hydrocarbonsfrom a wellbore prior to cementing or prior to introduction ofcompletion brine during completion operations.

Example 13

VertecBio Gold #1 and SoyGold 2000 fluid systems were tested todetermine the ability to dissolve or disperse paraffin and asphaltenedeposits in comparison to xylene and Paravan 25.

Paraffin or asphaltene solid (0.5 grams) was added to a container with a50 cc volume of fluid system. The container was then covered andincubated in a 175° F. water bath for a period of 45 minutes. After the45 minute incubation period, the jars were removed from the water bathand the fluid system was filtered through a Whatman filter to collectthe remaining solids. After the total fluid volume was filtered, theremaining solids were washed with water and dried at 120° F. Theremaining solid weight from each test was determined and the weightswere utilized to calculate the percent solids dissolved. Table V detailsthe results of the paraffin and asphaltene dissolution tests conductedwith the VertecBio Gold #1 and the SoyGold 2000 in comparison to xyleneand Paravan 25 solvents.

TABLE V Paraffin and Asphaltene Dissolution Tests at 175° F. for 45Minutes Solvent Weight % Solid System Dissolved Asphaltene Xylene 94%Asphaltene Paravan 25 92% Asphaltene SoyGold 2000 92% AsphalteneVertecBio Gold #1 94% Paraffin Xylene 44% Paraffin Paravan 25 46%Paraffin SoyGold 2000 24% Paraffin VertecBio Gold #1 30%

VertecBio Gold #1 dissolved the test asphaltene solids as effectively asxylene and slightly more efficiently than the Paravan 25. In theparaffin solids dispersion tests, VertecBio Gold #1 dissolved a lowerpercentage of paraffins than the xylene or Paravan 25 solvent system.However, it was active on the paraffin material.

Thus, VertecBio Gold #1 was very effective in removal of pipe dope, as adisplacement cleaning spacer for OB and SOBM muds, and indissolution/dispersion of paraffin solids as a neat solvent. TheVertecBio Gold #1 was more efficient in these applications than theSoyGold 2000 alone.

The bio-based system fluids are 100% biodegradable to carbon dioxide andwater have low volatile organic compounds (VOCs) and have low aquatictoxicity. They are useful in environmentally sensitive areas especiallywhen used to remove and disperse or dissolve asphaltenes and paraffinsfrom producing oil and gas wells.

Examples 14-17

A microemulsion product containing the water-insoluble VerticBio Gold #1illustrates reduction in costs of the treatment spacer system. Themicroemulsion was prepared containing 50% ethyl lactate and 50% soybeanmethyl ester solvent. The blend was then mixed with an emulsifier blendof Synperonic 91/6 and Monawet MO-70R. Synperonic 91/6 was mixed withthe Monawet MO-70R at volume ratios of 40/60, 50/50 or 60/40. Thisemulsifier was then mixed at a ratio of 25 volume % with solvent andwater at ratios of approximately 30% and 45% for the total microemulsionpackage system.

The following formulas were blended in a Waring blender at the highshear setting with a ten-minute mixing period after the addition of eachcomponent. After the addition of the last component (water), the finalcomposition was mixed for an additional ten minutes to ensure adequatehigh energy mixing for the formation of a microemulsion. After mixing,the solution were poured into a glass jar and allowed to sit overnight.The solutions were then evaluated for stability and clarity to determineif a microemulsion had been mixed.

Example 14 1000 cc Total Volume

A) 125 cc of Synperonic 91/6 25% Total Volume 125 cc of Monawet MO-70RB) 150 cc of Ethyl Lactate 30% Total Volume 150 cc Soybean Methyl Ester(The two solvents were mixed initially and added as one solvent system.)C) 450 cc of Water 45% Total Volume

Example 15 1000cc Total Volume

A) 125 cc of Synperonic 91/6 25% Total Volume 125 cc of Monawet MM-80 B)150 cc of Ethyl Lactate 30% Total Volume 150 cc of Soybean Methyl Ester(The two solvents were mixed initially and added as a single solution.)C) 450 cc of water 45% Total Volume

Example 16 1000 cc Total Volume

A) 100 cc of Synperonic 91/6 25% Total Volume 150 cc of Monawet MM-80 B)150 cc of Ethyl Lactate 30% Total Volume 150 cc of Soybean Methyl Ester(The two solvents were mixed initially and added as a single solution.)C) 450 cc of water 45% Total Volume

Example 17 1000 cc Total Volume

A) 150 cc of Synperonic 91/6 25% Total Volume 100 cc of Monawet MM-80 B)150 cc of Ethyl Lactate 30% Total Volume 150 cc of Soybean Methyl Ester(The two solvents were mixed initially and added as a single solution.)C) 450 cc of Water 45% Total VolumeFormulation Stability Tests

Evaluation of the formulations of Examples 14-18 showed thatformulations of Examples 15-18 were cloudy with a destabilized layer ofemulsifier on top of the solutions. However, the formulation of Example14 was clear with no component breakout evident. This solution remainedclear and stable for a six-week room temperature incubation period.

Heat/Thaw Stability Tests

Heat and freeze stability tests were conducted on the formulation ofExample 14 to determine if the microemulsion would destabilize withextreme temperatures. The formulation was cooled down to a temperatureof 40° F. for a two hour period to check for fluid crystallization. Nocrystallization or freezing of the formulation was observed. Theformulation of Example 14 was removed from the refrigerator and heatedto 175° F. for a period of three hours to check for high temperatureinstability. No component breakout or instability was observed afterincubation at 175° F. for three hours.

Mud Displacement Study

A mud displacement cleanup study was conducted with the microemulsion ofExample 14 to determine how well it displaced the 17.0 ppg Synteq oilbased mud from the sleeve of the Chan 35 viscometer. The displacementstudies showed that at 140° F. after a ten minute reaction period at 200rpm, the microemulsion formulation of Example 14 removed 89% of the 17.0ppg Synteq oil based mud from the viscometer sleeve. This test showedthe microemulsion of Example 14 performed as well or better than thepure solvent in removing the 17.0 ppg Synteq oil based mud from the Chan35 sleeve under the same temperature, time and rpm conditions. Theprevious test results show the pure solvent under the same testconditions removed approximately 81% of the 17.0 ppg Synteq oil basedmud from the Chan 35 sleeve.

From the foregoing, it will be observed that numerous variations andmodifications may be effected without departing from the true spirit andscope of the novel concepts of the invention.

1. A method of treating an oil or gas well having a wellbore, wellcasing, production equipment or recovery equipment which comprisesintroducing into the wellbore, well casing, production equipment orrecovery equipment a microemulsion having a discontinuous phase of ablend of a C₁-C₄ ester of a C₁₆-C₂₀ fatty acid and an emulsifier.
 2. Themethod of claim 1, wherein the microemulsion further comprises asurfactant.
 3. The method of claim 2, wherein the surfactant isnonionic.
 4. The method of claim 3, wherein the weight percent of thenonionic surfactant based on the total weight of C₁-C₄ ester of aC₁₆-C₂₀ fatty acid and surfactant is between from about 1 to about 8percent.
 5. The method of claim 3, wherein the nonionic surfactant isselected from the group consisting of octylphenol polyethylene oxideethers, nonylphenol polyethylene oxide ethers, linear alcoholpolyethylene oxide ethers and sorbitan monooleate polyethylene oxideethers.
 6. The method of claim 1, wherein the fatty acid of the ester ofthe C₁₆-C₂₀ fatty acid is an oil selected from the group consisting ofcorn, mustard, niger seed, olive, peanut, poppy seed, rapeseed,safflower, sesame, soybean, sunflower seed and wheat germ.
 7. The methodof claim 1, wherein the C₁-C₄ ester of a C₁₆-C₂₀ fatty acid is a C₁₆-C₂₀fatty acid methyl ester.
 8. The method of claim 7, wherein the C₁-C₄ester of a C₁₆-C₂₀ fatty acid is soybean methyl ester.
 9. The method ofclaim 1, wherein the method comprises introducing the microemulsion intoan oil or gas producing well penetrating a geological formation andstimulating the formation.
 10. The method of claim 9, wherein themicroemulsion further comprises a proppant.
 11. method of claim 1,wherein, subsequent to introduction of the microemulsion into thewellbore, well casing, production equipment or recovery equipment,unwanted deposits are removed therefrom.
 12. The method of claim 11,wherein the unwanted deposits removed from the wellbore, well casing,production equipment or recovery equipment are selected from the groupconsisting of asphaltenes, hydrogen sulfide, paraffins, scales, fines,sulfur, heavy oil by-products, water blocks, drilling fluids, cementfiltrates, kill fluids, pipe dope, hydrocarbon emulsions, oil based mudsand/or synthetic oil based muds.
 13. The method of claim 11, wherein themicroemulsion is introduced into the wellbore, well casing, productionequipment or recovery equipment through production or coiled tubing. 14.The method of claim 1, wherein the microemulsion is introduced into thewellbore, well casing, production equipment or recovery equipment anddrilling muds are removed therefrom and further wherein the drillingmuds are removed prior to cementing of the wellbore or prior tointroduction of a completion brine into the wellbore.
 15. The method ofclaim 14, wherein the drilling muds are selected from the groupconsisting of oil based muds and synthetic oil based muds.
 16. Themethod of claim 1, wherein the microemulsion is introduced into thewellbore, well casing, production equipment or recovery equipment whichcontains a well treating gelled fluid and further wherein themicroemulsion, acting as a breaker catalyst, activates a gel breakerwhich is present in the wellbore, well casing, production equipment orrecovery equipment thereby reducing the viscosity of the well treatinggelled fluid.
 17. The method of claim 1, wherein the microemulsion is adisplacement spacer or a spearhead fluid.
 18. A method of removing pipedope, hydrocarbons, drilling muds, hydrogen sulfide, scales, fines,sulfur, heaving oil by-products, water blocks, cement filtrates, killfluids, paraffins and/or asphaltenes from surface equipment or downholeequipment which comprises introducing onto the surface of the surfaceequipment or downhole equipment a microemulsion having a discontinuousphase of a blend of a C₁-C₄ ester of a C₁₆-C₂₀ fatty acid and anemulsifier.
 19. The method of claim 18, wherein the fatty acid of theester of the C₁₆-C₂₀ fatty acid is an oil selected from the groupconsisting of corn, mustard, niger seed, olive, peanut, poppy seed,rapeseed, safflower, sesame, soybean, sunflower seed and wheat germ. 20.The method of claim 18, wherein the microemulsion further comprises asurfactant.
 21. The method of claim 18, wherein the C₁-C₄ ester of aC₁₆-C₂₀ fatty acid is a C₁₆-C₂₀ fatty acid methyl ester.